Table



anthraquinone chromophoric group types.

United States Patent 3,125,564 DlI-IALO-TRIAZINYLAMINO-AZO AND ANTHRA-QUIN ONE DYESTUFF COMPOSITIONS STABI- LIZED WITH MIXTURES 0F ALKALIMETAL PHOSPHATES Robert Norman Heslop and William Ellio t Stephen,Manchester, England, assignors to Imperial Chemical Industries Limited,London, England, a corporation of Great Britain No Drawing. Filed Jan.9, 1959, Ser. No. 785,977 4 Claims. (Cl. 260-153) This invention relatesto improvements in dyestuffs, in particular dyestuff compositions forcommercial use. More specifically this invention is directed to noveldyestulf compositions of dyestuffs containing a C-halogen-1:3:5-triazine ring stabilized by the presence of a mixture ofwater-soluble phosphate salts, which provide, in aqueous solution, abuttered pH range of from about pH 6 to pH 8.

This application is a continuation-in-part of copending applicationsSerial Nos. 549,175, now U.S. Patent 2,907,- 762; 549,176, nowabandoned; 549,177, now U.S. Patent 2,892,828; 549,178, now U.S. Patent2,892,829; 549,179, now U.S. Patent 2,892,830; 623,760, now U.S. Patent2,892,831; 634,662, now U.S. Patent 2,889,323; 646,526, now abandoned;652,684, now abandoned; 680,004, now abandoned; 709,453, now U.S. Patent3,004,022; 710,874, now abandoned; 737,221, now U.S. Patent 2,977,353;737,222, now U.S. Patent 2,951,836; 737,223, now abandoned; 741,996, nowU.S. Patent 3,087,924; 732,820, now U.S. Patent 2,892,671; 732,841, nowU.S. Patent 2,892, 670; 742,039, now U.S. Patent 2,951,070; 742,718;742,- 721, now abandoned; and 754,178, now U.S. Patent 3,- 057,844, thedisclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION There are now known a number of azo andanthraquinone dyestuffs which are characterized by having aC-halogen-1:3:5-triazine ring in their molecular structure. ByC-ha1ogen-1:3:5-triazine ring is meant a radical having the structuralformula:

where X represents a halogen atom (attached, as seen, to a nuclearcarbon atom of a 1:3:5-triazine ring). In the dyestuffs of presentinterest, at least one of the indicated free valencies of the other twocarbon atoms of the triazine ring is attached to an amino nitrogen atomsubstituted by at least one chromophoric group of the azo and One of thesaid free valencies may, alternatively, bond a second halogen atom to anuclear carbonjatom, or instead may be attached to any one of a numberof non-chromophoric groups, as will be mentioned at greater lengthhereinafter. It is convenient to refer to the subject class of dyestuffsas azo and anthraquinone dyestuffs containing at least one solubilizinggroup and a primary or secondary amino group carrying as N-substituent a1:3:5-triazine radical containing a halogen atom attached to a carbonatom of said triazine ring. Alternatively these dyestuffs may bereferred to as monoand di- (C-halogen)-1:3:5-triazin-2- ylamino-azo andanthraquinone chromophoric group-containing dyestuffs, it beingunderstood that in this nomenclature at least one ionogenic solubilizinggroup is present in the azo or anthraquinone chromophoric group.

ice

These monoand di-(C-halogen)-1:3 :S-triazin-Z-ylamino-azo andanthraquinone chromophoric group-containing dyestuffs have excellentproperties for coloring textile fabrics made from a Wide variety and offibers including cellulosic and protein fibers as well as various synthetic fibers such as nylon. The coloring process may be carried out inthe manner described in copending applications Serial Nos. 732,820;732,841; 680,009, now abandoned; 683,012, now U.S. Patent 2,950,165;585,957, now U.S. Patent 2,892,674; 652,681, now abandoned; 652,682, nowabandoned; 696,966, now U.S. Patent 2,940,812 and 664,511; now U.S.Patent 3,042,477. As pointed out in these copending applications, theresulting dyed or printed materials exhibit remarkably fastcharacteristics of great value.

The commercial value of the monoand di-(C-halogen) 1:3 :5 triazin 2ylatnino azo and anthraquinone chromophoric group containing dyestuffshas, however, met with the difficulty that these dyestuffs decompose onstorage within a few months under tropical conditions and thedi-(C-halogen) dyestuffs decompose appreciably under temperateconditions within the usual time from manufacture to delivery to and useby the dyer. This decomposition can lead to irregular and unsatisfactorydyeings or printings because, of course, the dyestuif per se is presentin less than the expected quantity or not at all, and foreign substancesare also present which interfere with the dyeing process.

In addition, the very preparation of the subject dyestuffs can beseverely hindered by this decomposition. Thus, the usual and convenientmode of preparation of these monoanddi-(C-halogen)-1:3:5-triazin-2-ylamino-azo and anthraquinonechromophoric group-containing dyestuffs is by reaction of an azo oranthraquinone chromophoric group-containing primary or secondary aminewith a dior tri-(C-halogen)-1:3z5-triazine ring compound to form thetriazinylamino structure, with loss of hydrogen halide. Atlernatively,an already formed and suitably substituted monoordi-(C-halogen)-123:5-triazin-2-ylamino compound may be reacted with adiazonium or cou- 1 pling compound to form an azo-chromophoricgroup-containing dyestuif. Other methods of preparation are alsopossible. In general, however, it is frequently desirable forpreparatory purposes to carry out the reaction involved in an aqueoussuspension or solution. Unfortunately, when water is present it hasfrequently been found that the desired product is obtained in low yieldand poor quality, due to decomposition involving, at least in part, thereplacement of the halogen attached to the triazine nucleous byhydroxyl, both during the reaction period and during the isolation ofthe dyestuff. Of course, the already mentioned storage decompositiontakes place Whether or not the dyestuff preparation was carried out inthe absence of water.

The prevention of such decomposition and stabilization of the subjectdyestuffs is therefore a serious problem which has been a contributoryfactor to the previous lack of development of this segment of thedyestuff art.

OBJECTS OF THE INVENTION Accordingly, it is an object of this inventionto provide novel stabilized dyestutf compositions which contain as theprincipal coloring material therein a monoor di-(C-hal0gen)-1:3:5-triazin-2-ylamino-azoor anthraquinone-chromophoric group-containingdyestufi and as a stabilizer therefor a mixture consisting essentiallyof water-soluble phosphate salts, which phosphate salt mix ture has, inaqueous solution a buffered pH of from 6 to 8.

It is a further object of this invention to provide a process forstabilizing dyestufi compositions which contain as the principalcoloring matter therein a monoor di- (C-halogen)-1 3S-triazin-Z-ylamino-azo or anthraquinone chromophoric group containingdyestufi wherein before or during the preparation, isolation orformulation of such dyestuif there is added thereto, as a stabilizer, amixture of water-soluble phosphate salts, which phosphate salt mixturehas, in aqueous solution, a buffered pH of from 6 to 8.

Additionally, it is an object of this invention to provide novelstabilized dyestulf compositions which contain as the principal coloringmaterial, in an amount of at least about 20% by weight therein, a monoordi-(C-halogen)- 1 :3 :S-triazin-Z-ylamino-azooranthraquinone-chromophoric group-containing dyestuff and as a stabilizertherefore at least 1%, by weight of the composition, of a mixture ofwater-soluble phosphate salts, which phosphate salt mixture has, inaqueous solution, a pH of from 6 to 8, and wherein there may also bepresent inert materials.

Other objects of this invention will be apparent from the followingdescription thereof.

DESCRIPTION OF THE INVENTION As hereinbefore stated, the presentinvention provides a stabilized dyestuif composition whereas thedyestuffs in the absence of the presence of the stabilizer willdecompose. It is a feature of this invention that to the best of ourknowledge there are no dyestuffs in the class of azo and anthraquinonedyestuffs containing at least one ionogenic solubilizing group and aprimary or secondary amino group carrying a N-substituent, a1:3:5-triazine radical containing a halogen atom attached to a carbonatom of said triazine ring which are not stabilized in the compositionof the present invention. Nor are there, to our knowledge, anysubstituents which may be present on such azo and anthraquinonedyestuffs which interfere with the stabilized characteristics of thecomposition.

DESCRIPTION OF AZO AND ANTHRAQUINONE CHROMOPHORIC GROUPS Thus among thedyestuffs which may be used in the practice of this invention are thosewhich contain, as an aminoazo chromophoric group attached to the2-position on the triazine ring, the amino radicals from the productobtained by coupling diazotized aniline with1:8-aminonaphthal-3:6-disulfonic acid (so that the azo group is attachedin the 7-position), or by coupling diazotized metanilic acid witho-anisidine; or as the aminoanthraquinone chromophoric group attached tothe said 2-position, amino radicals from compounds such as 1-amino-4-(4-aminoanilino -anthraquinone-2 3 -disulfonic acid.

Other anthraquinoneamino derivatives which may be used include1-amino-4-(3 '-aminoanilino)-anthraquinone-2,4'-disulfonic acid,

1-amin0-4 2'-methyl-5'-aminoanilin) -anthraquinone-2,4-

disulfonic acid,

1-amino-4-( 2'-methyl-3 '-aminoanilino -anthraquinone-2,

disulfonic acid,

1-amino-4- (4' 4"-aminophenylazo -anilino -anthraquinone-2,3"-disulfonicacid,

1-amino-4- 3 -carboxy-4-aminoanilino) -anthraquinone-2- sulfonic acid,and

1-amino-4- 4'- (4"-aminophenyl) -anilino -anthraquinone- 2,3"-disulfonic acid.

In each instance, the aromatic ring carried by the 4-amino group on theanthraquinone nucleous may be substituted at any of the availablepositions by radicals such as lower alkyl, lower alkoxy, halogen,halogen-substituted lower alkyl and lower alkoxy, hydroxy-substitutedlower alkyl and lower alkoxy, and/or additional ionogenic solubilizinggroups, and including similarly substituted phenyl radical substituents.

Further anthraquinone chromophoric amino radicals which may be presentinclude 1-amino-4- (4-aminoanilino -anthraquinone-2: 3 S-trisulfonicacid,

1-amino-4-(4'-(4-aminophenylazo)-anilino)-anthraquinone-2 2"S-trisulfonic acid,

1-amin0-4-(4-aminoanilino) -anthraquinone-2 3 6-trisulfonic acid,

l-amino-4-(4'-amino-3'-carboxyanilino)-anthraquinone- 2:5-disulfonicacid,

1-amino-4- 3 -aminoanilino -anthraquinone-2 4 5-trisulfonic acid, and

1-amino-4- (4'- 4-aminophenyl -anilino -anthraquinone-2:3":5-trisulfonic acid.

There may also be used 1-amino-4-(4-methylaminoanilino)-anthraquinone-23 5- trisulfonic acid,

1-amino-4- (4'-methylaminoanilino -anthraquinone-2 3'- disulfonic acid,

1-amino-4- (4-n-butylaminoanilino -anthraquinone-2 3 disulfonic acid,

1-amino-4- (4-cyclohexylaminoanilino) -anthraquinone- 2:3'-disulfonicacid,

1-amino-4- 4-methylamino-3 -carboxyanilino -anthraquinone-2-sulfonicacid, and

1-amino-4- 3 fi-hydroxyethylamino -anilino) -anthraquinone-2S-disulfonic acid,

1-amino-4- 4'-methylamino -anilinoanthraquinone-Z-sulfonic acid,

1-amino-4-(4-aminoanilino)-anthraquinone-2 3-disulfonic acid,

1-amino-4-anilino-anthraquinone-2 S-disulfonic acid,

l-amin0-4-(4-aminoanilino)-anthraquinone-2 5 -disulfonic acid,

1-amino-4-(4-(4"-aminophenylazo)-anilino)-anthraquinone-2 3S-trisulfonic acid,

l-amino-4- (4-aminoanilino -anthraquinone-Z-sulfonic acid,

1,4-diaminoanthraquinone-Z-sulfonic acid,

1 5-dihydroxy-4,8-di (4'-aminoanilino) -anthraquinone- 2:6-disulfonicacid,

6- (4'-aminoanilino -2- 2-hydroxyphenyl-anthrapyrimidine-3:3"-disulfonic acid, and

1-{3-sulfato-isopropylamino-4- (4'-aminoanilino)-anthraquinone-3'-su1fonic acid.

In 'addition to these typical anthraquinone radicals, among the aminoazochromophoric group-containing radicals which may be used arel-amino-7-(phenylazo)-8 hydroxy-naphthalene-3:6-disulfonic acid, and theaminoazo compounds obtained by coupling diazotized metanilic acid with1-acetylamino-8-naphthol-3 6-disulfonic acid, by coupling diazotizedp-aminoacetanilide or diazotized 2- amino-4-sulfophenylether withl-amino-S-hydroxynaphthalene-3 :6-disulfonic acid, and

1-amino-8-hydroxy-7-(phenylazo) -naphthalene-3 6: 6-

trisulfonic acid,

1-amino-8-hydroxy-7- 2 4'-dimethylanilino) -naphthalene-3 66'-trisulfonic acid,

1-amino-8-hydroxy-7- 3 '-chloro-4'-methylphenylazo) naphthalene-3 6:6'-trisulfonic acid,

1-amino-8-hydroxy-7-(4'-methylphenylazo -naphthalene-3 :6:6'-trisulfonic acid,

1-amino-8-hydroxy-7- (4-chloro-3 '-methylphenylazo naphthalene-3 66-trisulfonic acid,

1-amino-8-hydroxy-7-(4-chlorophenylazo)-naphthalene-3.6:2'-trisulfonicacid,

1-amino-8-hydroxy-7-phenylazon aphthalene-3 6 2' 5 tetrasulfonic acid,

1-amino-8-hydroxy-7- (3 '-trifiuoromethyl-phenylazo naphthalene-3 :62'-trisulfonic acid,

1-amino-8-hydroxy-7- 3 -4'-dichlorophenylazo) -napl1- thalene-3 :66-trisulfonic acid,

2-amino-7- (2 4'-dimethylphenylazo -8-naphthol-6 6'- disulfonic acid,

2-methylamino-7- (4'-methoxyphenylazo -8-naphthol- 2'z6-disulfonic acid,

2-amino-7-(3-methyl-4'-chloropl1enylazo)-8-naphthol- 6:6'-disulfonicacid,

Z-amino-7-p-tolylazo-8-naphthol-6 6-disulfonic acid,

2-amino-7-phenylazo-8-napl1thol-2' 5 6-trisulfonic acid,

2-amino-7- (4'-chlorphenylazo -8-naphthol-6 6'-disulfonic acid,

2-amino-7-m-tolylazo-8-n aphthol-6 6-disulfonic acid,

2-amino-7-(3-chloro-p-tolylazo)-8-naphthol-6:6-

disulfonic acid,

2-amino-7-o-tolylazo-8-naphthol-5 6-disulfonic acid,

2-amino-7- 4-metl1oxyphenylazo -8-naphthol-2' 6- disulfonic acid,

2-amin0-7- 2'-o-tolyloxyphenylazo-8-naphthol-5 6- disulfonic acid,

2-methylamino-7- a-naphthylazo) -8-naphthol-4 6- disulfonic acid,

2-methylamino-7-(a-naphthylazo) -8-naphthol-3 6' 6- trisulfonic acid,

2-methylamino-7- a-naphthylazo -8-naphthol-3 6:7

trisulfonic acid,

2-methylamino-7-(B-naphthylazo) -8-naphthol-1' :5: 6-

trisulfonic acid,

2-methylamino-7- a-naphthylazo -8-naphthol-6 6- disulfonic acid,

2-methylamino-7- ot-naphtholazo) -8-naphthol-6 7- disulfonic acid,

2-methy1amino-7-(fi-naphthylazo) -8-naphthol-3 6' 6- trisulfonic acid,

2-methylamino-7- 2'-methoxy-5 '-chlorphenylazo -8- naphthol-36-disulfonic acid,

2-methylamino-7-(2'-methoxy-3'-chlorphenylazo)-8- naphthol-5'6-disulfonic acid,

2-methylamino-7-phenylazo-8-naphthol-2 6-disulfonic acid, and

2-methy1amino-7-(p-methoxyphenylazo)-8-naphthol- 2z6-disulfonic acid.

Thus, there may be used the aminoazo radicals obtained by coupling thediazonium salt of a primary aromatic amine such as aniline, mandp-toluidines, xylidines, o-, mand p-anisidine, monoorpolychloroanilines, aniline 2-, 3- and 4-sulphonic acids,

2 4-dimethylaniline-6-sulphonic acid,

4-chloro-5-methylaniline-2-sulphonic acid,

5-chloro-4-methylaniline-2-su1phonic acid,

aniline-2 S-disulphonic acid,

4-methylaniline-Z-sulphonic acid,

3-methylaniline-6-sulphonic acid,

4-methoxyaniline-Z-sulphonic acid,

2: 5 -dichloroaniline-4-sulphonic acid,

2-aminotoluene-4-sulphonic acid,

aniline 2-, 3- and 4-carboxylic acids,

4-aminodiphenyl-3- and -4'-sulphonic acids,

1- or 2-aminonaphthalene,

1-aminonaphthalene-4-, 5-, 6- and 7-monosulphonic acids,

2-aminonaphthalene-326 and 3:7-disulphonic acids,

2-aminonaphtha1ene-1:5-, 4:8-, 6:8-, 5:7- and 3:6-disulfonic acids andZ-naphthylamine 326:8 trisulphonic acid, and similar alkyl, alkoxy, haloand acylamido substituted compounds, with a coupling component such as2-amino-8-naphthol-6-sulphonic acid,Z-methylamino-8-naphthol-6-sulphonic acid,Z-methylamino-l-chloro-8-naphthol-6-sulphonic acid,2-amino-8-naphthol-3:6-disulphonic acid and2-amino-3-carboxy-8-naphthol-6-sulphonic acid.

The corresponding Z-acetylamino and 2-formamido-compounds may also beused as coupling components.

In addition, as aminoazo chromophoric groups there may be used the aminoradicals obtained from sulfophenylnaphtholamines provided by coupling adiazotized primary aromatic amine such as aniline-Z-sulphonic acid,

aniline 2:5-disulphonic acid,

2 4-dimethylaniline-6-sulphonic acid,3-aminobenzotrifluoride-4-sulphonic acid,4-chloro-5-methylaniline-2-sulphonic acid,5-chloro-4-methylaniline-Z-sulphonic acid,3-acetylaminoaniline-6-sulphonic acid, 4-acetylaminoaniline-2-sulphonicacid, 4-chloroaniline-2-sulphonic acid,

3 :4-dichloroaniline-6-sulphonic acid, 4-methylaniline-2-sulphonic acid,3-methylaniline-6-sulphonic acid,

2 4-dimethoxyaniline-6-sulphonic acid, 4-methoxyaniline-Z-sulphonic acidand S-methoxyaniline-Z-sulphonic acid, with2-amino-5-naphthol-7-sulfonic acid andN-substituted-2-amino-5-naphthol-7-sulfonic acids,

(optionally with a later removed N-acyl structure) particularlyN-alkyl-2-amino-5-naphthol-7-sulfonic acids, in the 6-position. Suchazoamino dyestuffs include 2-amino-5-hydr0xy-6-phenylazo-naphthalene-27-disulfonic acid,

2-amino-5-hydroxy-6- (p-tolylazo) -naphthalene-2' 7- disulfonic acid,

2-amino-5-hydroxy-6- (3 -methyl-4-chlorophenylazo naphthalene-2'7-disulfonic acid,

2-amino-S-l1ydroXy-6-(4-chlorophenylazo)-naphthalene-2 7-disulfonicacid,

2-amino-5-hydroxy-6-phenylazo-naphthalene-Z 5 7- trisulfonic acid,

Z-methylamino-S-hydroxy-6-phenylazonaphthalene- 2':7-disulfonic acid,

2-amino-5-hydroxy-6-(3-chloro-4-methylphenylazo)- naphthalene-27-disulfonic acid,

2-amino-5-hydroxy-6- (5 '-methoxyphenylaz0 -naphthalene-2:7-disulfonicacid, and

2-a1nino-5-hydroxy-6- 5 -methylpl1enylazo) -naphthalene-Z' 7-disulfonicacid.

In the just named compounds, the amino group, which eventually becomesthe Z-ylamino group on the triazine ring, was attached directly to thenaphthol nucleus linked in turn to the azo radical. This is notnecessary since there may be equally well used in this invention thoseazo dyestuffs where there is a bridging radical between the nucleus andthe amino group. Such dyestuffs include 1-(3 '-aminobenzamido)-7-phenylazo-8-naphthol-2 :3 :6-

trisulfonic acid,

1- 3 '-aminobenzamido -7-phenylazo-8-naphthol-2 5 3"6:-tetrasulfonicacid,

1-(4-aminobenzamido)-7-phenylazo-8-naphthyl-2 3 :6-

trisulfonic acid,

1-( 3 -aminobenzamido) -7- 3 "-chloro-4"-methyl-phenylazo)-8-naphthol-6" 3 :6-trisulfonic acid,

1- 3 '-aminobenzamido) -7- 4"-methylphenylazo -8- naphthols-2" 3:6-trisulfonic acid,

1- 3 '-aminobenzamido -7- 4-methoxyphenylazo) -8- naphthol-3 36-trisulfonic acid,

1- (3 -aminobenzamido -7- 3 4"-dichlorophenylazo) -8- naphthol-6" 36-trisulfonic acid,

1-( 3 -aminobenzamido -7- 3 "-methylphenylazo -8- naphthol-6" :3:6-trisulfonic acid,

I-( 3 -aminobenzamido -7- ,H-naphthylazo -8-naphthol- 4-" 5" 36-tetrasulfonic acid,

1- 3 "-aminobenzamido -7- (/3-naphthylazo -8-naphtholl 3 :6-trisulfonicacid,

1- (3 "-aminobenzamido) -7- a-naphthylazo) -8-naphthol- 2":3:6-trisulfonic acid,

1- 3 -aminobenzamido -7- 4'-chlorophenylazo) -8-naphthol-2" 36-trisulfonic acid,

1- (3 -aminobenz-N- (n-butyl)-amido) -7-phenylaZo-8-naphtl10l-2:36-trisulfonic acid,

1- (3 '-aminobenzamido) -7-phenylazo-8-naphthol-2" 3 :6-

trisulfonic acid, and

1-( 3 '-aminobenzamido) -7-(3 -trifluoromethylphenylazo)-8-naphtl1ol-2":3 :6-trisulfonic acid.

That is, there may be used those amino azo compounds formed by couplinga diazotized primary aromatic amine such as orthanilic acid,

sulphanilic acid,

aniline-2 S-disulphonic acid,

4-chloroaniline-Z-sulphonic acid,

5-chloro-4-methylaniline-Z-sulphonic acid,

4-methylaniline-Z-sulphonic acid,

4-chloro-5-methylaniline-Z-sulphonic acid, 5

3-amino-4-sulphonbenzotrifluoride,3 :4-dichloroaniline- 6-sulphonicacid,

4-aminoanisole-3-sulphonic acid,

3-arninoanisole-4-sulphonic acid,

1-naphthylamine-Z-sulphonic acid,

2-naphthylamine-3 :6-disulphonic acid and Z-naphthylarnine-l-sulphonicacid (which may also be substituted by such groups as halogen, phenoxy,nitro, sulfamyl or monoor disubstituted sulfamyl, carboxylic acid,carboxylic ester, carbamyl or monoor disubstituted carbamyl groups inaddition to further sulfo radicals) with an amino coupling componentsuch as 1-(3-amino-benzoylamino)-8-hydroxynaphthalene-3:6- and4:6-disulphonic acids, 1-(4-aminobenzoylamino) 8-hydroxynaphthalene-3z6-and 4:6-disulphonic acids, 1-(3-aminobenzoylamino)-8-hydroxynaphthalene-2:4-disulphonic acid and1-(3-aminobenzoylamino)-8-hydroXynaphthalene-6-sulphonic acid.

Again, the amino group may be alkylamino on the naphthalene ring in the1-position, as in compounds such as Thus, in general, the aminoazoradical may be that obtained from the compound formed by coupling adiazotized primary aromatic amine such as orthanilic acid,4-aminoanisole-3-sulphonic acid, anthranilic acid,

S-chloro-anthranilic acid, o-aminobenzenesulphonamide,o-aminobenzenesulphon-N-ethylanilide, o-aminobenzene-Z-alkylsulphone,S-nitroanthranilic acid, 5-nitro-2-aminobenzonitrile ando-aminobenzotrifiuoride to the 7-position of a 1:8-naphthol amine suchas 1-methylamino-8-hydroxynaphthalene-3 :6-disulphonic acid,1-ethylamino-8-hydroxynaphthalene-3 6-disulphonic acid,

1Q 1-n-butylamino-8-hydroXynaphthalene-3 :6-disulphonic acid,1-methylamino-8-hydroxynaphthalene-4 6-disulphonic acid,1-ethylamino-8-hydroxynaphthalene-4 6-disulphonic acid,1-n-butylamino-8-hydroXynaphthalene-4 6-disulphonic acid, and1-methylamino-, l-ethylamino, and 1-buty1amino-8-hydroxynaphthalene-6-sulphonic acids. The aromatic nucleons of'theprimary aromatic amine may also contain additional substituents such ascyano, sulfonamido, substituted sulfonamido, sulfone, and trifluoromethyl (particularly at the position ortho to the azo group) and alkylgroups such as methyl, alkoxy groups such as methoxy and ethoxy,trifluoromethyl groups, and halogen atoms such as chlorine and bromine.

Examples of aminoazo radicals wherein there is a bridging group betweenthe amino group and an arylazo group include those formed from suchcompounds as 1- (4'-amino-3 '-methylphenylazo) -benzene-2 S-disulfonicacid,

2-( 2' -methyl-4'-amino-5 -methoxyphenylazo -naphthalene-3 :6-disulfonicacid,

2-(2'-methyl-4-'-arninophe11ylazo)-naphthalene-3 :6-disulfonic acid,

2- 3 -rnethyl-4'-aminophenylazo) -naphthalene-3 6-disulfonic acid,

2-(4-( 1'-amino)-naphthylazo)-naphthalene-3 :6: 6-trisulfonic acid,

2- (4--N-methylamino-phenylazo) -naphthalene-3 6-disulfonic acid,

1- 2'-methyl-4'-arninophenylazo -benzene-2 4-disulfonic acid,

1- 2'-methyl-4'-aminophenylazo) -benzene-3 S-disulfonic acid,

1- 2-methyl-4'-aminophenylazo) -4-methylbenzene-2 6- disulfonic acid,

1- (2-methyl-4-arninophenylazo) -naphthalene-3 :6-disulfonic acid,

1- 2-methyl-4-arninophenylazo -naphthalene-3 :7-disulfonic acid,

2- 2-methyl-4-aminophenylazo -naphthalene-1 S-disulfonic acid,

2-(4-( 1-amino) -naphthylazo) -naphthalene-1 :5 7-trisulfonic acid, and

2- 2'-methy1-4-aminophenylazo -naphthalene-5 7-disulfonic acid.

Thus, the aminoazo radical may be provided by the compounds obtained bycoupling, for example diazotized aniline-2:4, 2:5- and 3:5-disulphonicacids, 4-aminotoluene-2:5-, 2:6- and 3:5-disulphonic acids,Z-aminotoluene-3 :S-disulphonic acid, 6-chloro-2-ami notoluene-3S-disulphonic acid, 4- and S-sulpho-Z-aminobenzoic acids,Z-aminoterephthalic acid, 1-naphthylamine-2:4-, 2:5-, 2:6-, 2:7-, 3 :6-,3:7-, 416-, 4:7- and 5:7-disulphonic acids and Z-naphthylamine-lzS',3:6-, 3:7-, 416-, 417-, or 5:7- disulphonic acids with, as couplingcomponent, for example, o-toluidine, m-toluidine, m-anisidine,3-amino-4- methoxy-toluene, 2: S-dimethylaniline, 2 S-dimethoxyaniline,N-methylor N-ethyl-o-toluidines, N-methylor N- ethyl-m-toluidines or1-naphthylarnine-6- or 7-sulphonic acids. There may also be used theN(omega-sulphomethyl) derivatives of such coupling components, the azocompounds so obtained being treated, for example by heating With diluteaqueous alkali, to remove the N-(omegasulphomethyl) grouping.

Still other aminoazo radicals are those provided by such compounds as2-'(2-methylphenylazo)-napl1thalene- 3:6:8-trisulfonic acid,2-(4'-a-arninonaphthylazo)-naphthalene-3 :6: 8 6'-tetrasulfonic acid,1-( 4-a-aminonaphthylazo)-naphth-alene-2:4:7:6'-tetrasulfonic acid and1- (2-methylphenylazo) -naph-thalene-2 4: 7-trisulfonic acid; that is,those compounds obtained by coupling diazotized tni-sulfonaphthylaminessuch as 1 aminonaphthalene- 2:4:6-, 2:4:7- and 2:5:7-trisulfonic acids,and Z-naphthylarnine-l :5 :7-, 3:6:8-, and 1:3:7-trisulfonic acids with,as coupling component, an amine such as o-toluidine, m-toluidine,3-amino-4-methoxytoluene, 2:5-dimethylaniline, m-anisidine,2:5-dimethoxyaniline, N-methyland N-ethy l-o-toluidines, N-rnethyl andN-ethyl-m-toluidines, and 1-naphthylamine-6- and 7-sulphonic acids.There may also the used the N-(omega-sulp homethyl) derivative of suchcoupling components, the azo compounds so obtained being treated, \forexample by heating with dilute aqueous alkali, to remove theN-(omega-sulphomethyl) grouping.

Still another type of aminoazo chromophoric group is that provided bycompounds such as 2- 3 '-aminophenylazo)l-hydroxy-8-acetylaminonaphthalene-3 :6 6'-trisul=fonic acid,

2- 3 -aminophenylazo) -1-hydroxy-8-etl1ylamino naphthalene-3 66-trisu1fonic acid,

2-( 3 -aminophenylazo) -1-hydroxy-8-phenylarnino naphthalene-3 66-trisulfonic acid,

2- 3 '-arninophenylazo l -hydroxy-8-ethylamino naphthalene-3 6:6-trisulfonic acid,

2- 3 '-aminophenylazo -1-hydroxy'-8-phenylaminonaphthalene-3 66-tnisulfonic acid,

2- 3 -aminophenylazo l-hydroxy-8-benzoylarninonaphthalene-3 66-t-risulfonic acid,

2- 3 -aminophenylazo -1-hydroxy-S-am-inonaphthalene- 3 6: 6-trisulfonicacid,

2- 3 '-aminophenylazo) l-hydroxy-S-phenoxyacetylaminonaphthalene-3 6:6'-trisulfonic acid,

2( 3 -aminopheny'lazo) -1-hydroxy-8-(2 4"-dichloro benzoylamino)-naphthalene-3 6 6-trisul fonic acid,

2- 3 '-aminophenylazo -1-hydroxyl-(4-toluenesulfonylarnino -3 6:6'-trisulfonic acid,

2- 3 -arninophenylazo l-hydroxy-S-phenylaminonaphthalene-4 6-disulfonicacid,

2- (3 -arninophenylazo l -hydroxy-8- 4"-toluenesulfonylamino)naphthalene-4 6 6-trisulfonic acid,

2- 3 -aminophenylazo) l-hydroxy-6-acetylaminonaphthalene-3 6'-disulfonicacid,

2- 3 '-aminopheny'lazo) -1-hydroXy-7-acetylaminonaphthalene-36'-disulfonic acid,

2- 3 -aminophenylazo -1-hydroxy-7-dimethylaminonaphthalene-3:6-disulfonic acid,

2- (3 '-aminophenylazo)-1-1ydroxy-7-(2-hydroxyethylamino)-napht1halene-3 6'-disulfonic acid,

2- 3 -aminophenylazo -1-hydroxy-S-carbethoxyaminonaphthalene-3 6:6'-ti'-isulfonic acid,

2- (4'aminophenylazo) l-hydroxy-6-acetylaminonaphthalene-3 :6-disulfonicacid,

2-(4-aminophenylazo) l-hydroxy-S- (2" :4"-dichlorobenzoylamino-naphthailene-3 6: 6'-trisulfonic acid,

2-(4'-aminophenylazo) -1-hydroxy-8-pheny1aminonaphthalene-3 66-trisulfonic acid,

2- 3 -amino4'-methyl-phenylazo l-hydroxy-S- benzoylaminonaphthalene-3 65 -trisul'fonic acid,

2-( 3 '-aminophenylazo) -1-hydroxy-S-aminonaphthalene- 3 :6:6-trisu1fonic acid,

2- 3 -aminophenylazo l -naphtho=l-4 6-disul fonic acid,

2- 3 -aminophenylazo) l-napht-hol-3 :6:6-t1'isulfonic acid,

2-(3-aminophenylazo)-1-naphthol-3 6: 8 6-tetrasulfonic acid,

1- 3 '-arninophenylazo -2naphthol-6 8 6-trisulfonic acid,

2-(4'-aminophenylazo) l-naphthol-Z' 4-disulfonic acid,

1-(4'-aminophenylazo -2-naphtho l-2' 6-disulfonic acid,

1- 4'-aminophenylazo -2-naphthol-2 S-disulfonic acid,

1-(4'aminophenylazo) -2-naphthol-2' 6 8-trisulfonic acid,

2- (4'-arninophenylazo) -8-ethoxyl-naphthol-Z 3 6- trisulfonic acid,

1- (4-amin0pheny1azo -2-naphthol-2 3 6-trisulfonic acid,

2-(3'-nitr0-4'-aminophenylazo)-1-hydroxy-8-aminonaphthalene-36-disulfonic acid,

1-(3-nitro-4'-aminophenylazo -2-naphthol-6 8-disulfonic acid,

2-(4-aminophenylazo) -1 :8-dihydroxynaphthalene- 3:6-disulfonic acid,

2-(4-aminophenylazo) -1 8-dihydroxynaphthalene- 2 3 6-trisulfonic acid,

2-(2'-methoxy-5-arnino-pl1enylazo)-7-(4"-carboxyphenylamino)-l-naphthol-4' 3-disulfonic acid,

2- 2'-methoxy-5 -amino-phenylazo) -8-4-toluenesulfonylarnino)-1-naphthol-3 :6-disulfonic acid,

2-(4-aminophenylazo)-6-dimethylamino-1-naphthol-3- sulfonic acid,

2- (4-amino-2-chlorphenylazo) -8-acetylamino-1- naphthol-3 6-disulfonicacid,

2- 4'-aminophenylaz0 -8-phenylamino- 1 -napl1thol- 2' 3 :5 -tr-isulfonicacid,

2- 4'-amino-3 -carb0xy'phenylazo) -8-benzoylamino- 1-naphthol-36-disulfonic acid,

2- 3 '-aminophenylazo) -8- (4" 6-dichloro-s-triazin- 2"-ylamino-1-naphthol-3 6 6-trisulfonic acid,

2- 3 -amin0phenylazo -8- (4-chloro-6-amino-s-triazin-2"-ylamino)-1-naphthol-3 6:6'-trisu=lifonic acid,

2-(3-aminopl1enylazo)-8-[3"-(4":6"'-dichloro-striazin-2"'-ylamino)benzoylamino] -1-naphthol- 3 :6 6-trisulfonic acid,

and 2-(3'-aminophenylazo)-8-[4"-ch1oro-6-(3-sulfophenylamino)-s-triaziin-2-ylamino l-naphthol- 3:6:6'-trisu lfonic acid.

Still further azoamino radicals are provided by the compounds obtainedby coupling diazotized primary aromatiic amine such as2-naphthylamine-l-sulfonic acid, 2-napht-hylarnine-3 6 8-trisulfonicacid, Z-naphthylamine- 3 6-disulphonic acid, 2-naphthylarnine-4:8-disulphonic acid, Z-naphthylarnine-S:7-disulphonic acid,2-naphthylamine-6:8-disulphonic acid, 2-naphthylamine-l :S-disulphonicacid, Z-naphthylamine-6-sulphonic acid, l-naphthylamine-4-sulphonicacid, l-naphthylamine-5-sulphonic acid, 1-naphthylamine-6-sulphonicacid, l-naphthylamine- 7-su=1phonic acid,1-naphthylarnine-3:6-disulphonic acid, l-naphthylamine-3:7-disulphonicacid, and Z-naphthylamine-1:5:7-trisulphonic acid withl-amino-S-naphthol- 3 6-disulfonic acid, 1-amino-8-naphth01-4:6-disulfonic acid or 1-arnino-8-napththol-6-sulionic acid.

Similarly, there may be used the metallized azoamino radicals such asare provided by the compounds obtained by coupling diazotized primaryaromatic amines such as 2-aminophenol-4-sulfonamide, Z-arrminophenol,5-nit ro-2- arninophenol, 4-sulphamyl-2-aminophenol,3-amino-4-hydroxy-acetophenone, 5-nitro-2-aminophenoxy'acetic acid,4-methyl-sulphamyl-Z-arninophenol, o-anisidine,4-diethylsulphamyl-Z-aminoanisole, 4-chloro-2-aminoanisole, 2:5-dimethoxyaniline, Z-amino-iso-phthalic acid, 4-chlor0-2- aminophenol,anthranilic acid, 4-ethanesulphonyl-2-aminophenol, Z-aminoterephthalicacid, and 4-nitro-2-aminophenol, with Z-amino-S-naphthol-7-sulfonicacid, 1- amino-S-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulphonic acid, Z-methylamino-S-naphthol-7-sulphonic acid,Z-methylamino-S-naphthol-6-sulphonic acid,l-amino-8-naphthol-4-sulphonic acid, and Z-butylamino-S-naphthol-6-sulphonic acid; followed by treatment with a copper-yieldingagent such as copper sulphate and enprammonium sulphate, by methods wellknown in themselves, for example by heating the copper-lfree compoundwith an aqueous solution of the copper-yielding agent. In those casesWhere the metallizable group of the copperfree compound is an alkoxygroup, the de-alkylating coppering is carried out advantageously using acuprammonium salt and usually by heating for several hours at about 100C. in an aqueous ammoniacal medium.

Other metallized azoamino radicals are those provided by the compoundsobtained by coupling a diazotized primary aromatic amine such as2-aminophenol-4z6-disulphonic acid, 4-nitro-2-a-minophenol-6-sulphonicacid, 6-chloro-Z-aminophenol-4-sulphonic acid,4-chloro-2-aminophenol-G-sulphonic acid, 1-amino-6-nitro-2-naphthol-4-sulphonic acid, 4-sulpho-2-aminobenzoic acid, 6-nitro-2-aminophenol-4-sulphonic acid, S-sulpho-Z-aminobenzoic acid,2-aminop'henol-4-sulp honic acid, 2-aminoanisole-4- s-ulphonic acid,-nitro-2-aminoanisole-4-sulphonic acid, and1-amino-2-naphthol-4-sulphonic acid with a naphthol such asZ-methylamino-S-naphthol-7sulphonic acid, 2-n-butylamino-S-naphthol-7-suiphonic acid, andZ-ethylamino-5-naphthol-7-sulphonic acid. To convert the copper-freecompounds to their complex copper compounds, the copper-free compoundsare againtreated with a copper-yielding agent such as copper sulphateand ouprammonium sulphate, the latter being preferably used forcoppering when the metallizable group is an aflkoxy group, by methodswell-known in themselves, for example by heating the copper-freecompound with an aqueous solution of the copper-yielding agent.

Still other metallized azoamino radicals are those provided by thecompounds made by' coupling a diazotized primary aromatic amine such as2-aminophenol-4-su-lphonmethylamide, 4-ethane sulphonyl-Z-arninophenol,4- nitro-2-aminophenol-6-sulpl1onic acid,6-nitro-2-aminophenol-4-sulphonic acid,4-chloro-2-aminophenol-6-sulphonic acid,6-ch1oro-2.-aminophenol-4-sulphonic acid, anthranilic acid,4-nitro-2-aminophenol, Z-aminophenol, 5- sulpho-Z-aminobenzoic acid,4-chloro-2-aminophenol, 2- aminophenol 4 sulphonamide, 2 aminophenol 2sulphonic acid, 4-nitro-2-aminobenzoic acid, Z-aminoterephthalic acid,4-methoxy-2-aminophenol, Z-methoxy- 1-aminonaphthalene-G-suiphonic acid,1-amino-6-ni-tro-2- naphthol-4-sulp'honic acid, 4-sulpho-2-aminobenzoicacid with a polysulfoamino-naphthol such as 1-amino-8- naphthol-36-disulphonic acid, 1-amino-8-naphthol-4: 6- disulphionic acid,2-amino-5-naphthol-l:7-disulphonic acid,1-ethylamino-8-naphthol-3:6-disu1phonic acid, 1(3'-aminobenzoyl)amino-8-naphthol-3:6-disulphonic acid, 1-butylamino-8-naphthol-3:6-disulphonic acid, Z-amino-S-naphthol-3z6-disulphonic acid, and 1-(4-aminobenzoyl)amino-8-naphthol-3:6-disulphonic acid. To convert the copper-freecompounds to their complex copper compounds, the copper-tree compoundsare again treated with a copper-yielding agent such as copper sulphateor cuprammonium sulphate the latter being particularly useful when adealkylative coppering is required, by methods well-known in themselves,for example by heating the copper-free compounds with an aqueoussolution of the copper-yielding agent.

In addition, disazoamino radicals may be used such as those provided bycompounds obtained by coupling a diazotized primary aromatic amine suchas 4-sulfamylaniline, 2-11aphthylamine-o-sulfonic acid aniline-2:5-disulphonic acid, 4-nitraniline-2sulphonic acid,Z-methoxyaniline-S-sulphonic acid, sulphanilic acid,4-methoxyaniline-Z-sulphonic acid, 2-naphthylamine-4:S-disulphonic acid,5-chloro4-methylaniline-6-sulphonic acid, metanilic acid,4-methylaniline-2-suiphonic acid, orthanilic acid, 6-chloro-4-methyl-aniline-3-sulphonic acid, Z-naphthylamine-6S-disuiphonic acid, Z-naphthylamine-S :7-disulphonic acid,6-chloro-4-aminoto-luene-3-sulphonic acid, 6-chloro-3-aminotoluene-4-sulphonic acid, aniline-2:4-disulphonic acid,6-nitr0-3-amino benzoic acid, 4-nitro4- amino stilbene-2 :2-disulphonicacid, and p-anisidine, with an aromatic amine such asm-toluidine,aniline, orthoanisidine, 2:5-dimethoxyaniline,1-naphthylamine-6-swlphonic acid, mtoluidine and ant-hranilic acid, andthen diazotizing the resulting azoarnine and coupling the diazonium saltwith an amino naphthol such as I-amino-S-naphthol- 3 :6-disulphonicacid, 1-amino-8-naphthol-4 6-disulphonic acid,l-ethylamino-8-naphthoi-3:G-disuiphonic acid and l-butylamino-8-naphthol-3:G-disulphonic acid. Where 14 i the second amine has agrouping such as methoxy, hy'- droxy, carboxy, or carboxymethoxy in aposition ortho to the attached azo group, metallized dyestuifs arepossible, and, especially the copper complexes, are particularlyvaluable.

The above-described amino radicals become, in the subject dyestuffs, the-2-ylamino group on the monoor dihalogeno triazine ring, as heretoforedescribed. The formation of the amino-triazine substituted material maybe simply visualized as reacting the (azo or anthraquinone) primary orsecondary amino group compound with a dior tri-halogeno triazine ring,with loss of hydrogen halide. This is in fact a frequently convenientmethod of preparation as described in the above-noted copendingapplications. However, the foregoing description is not to be construedas limiting the dystuffs which may be used in the practice of thisinvention to dyestuffs produced in such a fashion. Equally well, and asalso described in the above-noted copending applications, the dyestuffsmay be prepared by first forming a 2-ylamino-monoor dihalogeno triazineand thereafter introducing an azo or anthraquinone chromophoric group byreaction with the existing 2-ylamino group or substituent thereon. Itwill be appreciated that this method still results in having ananthraquinoneor azo-amino radical as already described attached to thetriazine ring at the 2-position.

It is also within the scope of this invention to have more than onetriazin-Z-ylamino group in the subject dyestuffs as where the azo oranthraquinone chromophoric group has two or more primary or secondaryamino groups and these are each reacted with a dior tri-halogenotriazine ring, either successively or simultaneously.

It is further within the scope of this invention to employ dyestuffs inthe composition which have two azoand/ or anthraquinone-chromophoricgroups substituted on a monohalogeno diaminotriazine ring. That is, thedyestufis wherein a trihalogeno triazine (cyanuric trihalide) is reactedsuccessively or simultaneously with two mols of the 2120- oranthraquinone-amine, either the same or ditferent. For ease ofpurification and isolation, if two difiI'erent chromophoric groupsattached to two different amino groups on the same triazine ring aredesired, it is preferred to prepare such mono-C-halogeno-triazin-2:4-diylamino dyestuffs by first introducing one of the desiredchromophoric-amino groups and then introducing the secondchromophoric-amino group (again, either by the reaction of the azooranthraquinone amine with the C-halogeno triazine with loss of hydrogenhalide, or by introduction of a chromophoric group by reaction with anexisting triazinylamino structure, as for instance by azo-couplingreaction with a benzenoidamino group on the triazine ring).

However, it will be appreciated that while the immediately foregoingdescription, as well as that of the mentioned copending applications andthe examples presented hereinafter, will advise those skilled in the artof the scope of the applicability of this invention, i.e. generally toany azo or anthraquinone dyestulf containing at least one solubilizinggroup and a primary or secondary amino group carrying as N-substituent a1:3:5-triazine radical containing a halogen atom attached to a carbonatom of said triazine ring, and of the methods available for formingthis dyestuff structure, the actual reaction scheme employed forbringing the organic radicals into interaction forms no part of thescope of this invention. On the other hand, it is a part of thisinvention to carry out such reaction in the presence of the stabilizerso that the latter is present during and after the formation andisolation of the dyestufi, as will be set forth more fully hereinafter.

DESCRIPTION OF THE TRIAZINE RING The monoor di-halogeno triazine ringforming a part of the subject dyestuffs which may be used in thisinvention must be clearly distinguished from trichlorocyanuric acid. Thelatter compound has the structure:

II C whereas cyanuric trichloride has the structure where X is halogen.Thus, in the present invention, the dyestuffs employed are those havingthe triazine ring (i.e. unsaturated with three conjugated double bonds)with the halogen atoms directly attached to a nuclear carbon atom.

At least one of the halogen atoms will be directly replaced by the azoor anthraquinone chromophoric groupcontaining amino radical. Themonohalogeno dyestuffs may be formed by having two of the halogen atomsdirectly replaced by an azo or anthraquinone chromophoricgroup-containing amino radical. Alternatively, there may be usedmonohalogeno triazine dyestuffs having a single azo or anthraquinonechromophoric group-containing amino radical, with a second halogen atomdirectly replaced by a different radical. Such other radicals (which maybe referred to as 4-position radicals, indicating the position ofattachment to the triazine ring) may include alkyl groups such asmethyl, ethyl, propyl, butyl, etc. (including straight andbranched-chain radicals), aryl groups such as phenyl, or naphthyl,alkoxy groups such as methoxy, ethoxy, butoxy, aryloxy groups such asphenoxy, and cresyloxy, aralkyloxy groups such as benzyloxy, aralkyl,cycloalkyl, alkylmercapto such as methyl mercapto, arylmercapto such asphenylmercapto, amino, alkylamino, dialkylamino, arylamino,aralkylamino, cycloalkylamino, aralkyl, etc. A Wide variety of radicalsWithin each class may be used; for instance, suitable primary andsecondary amines which may be used to introduce a nonhalogeno 4-positionradical include methylamine, butylamine, diethylamine,fl-hydroxyethylamine, cyclohexylamine, aniline, fl-naphthylamine,metanilic acid, 2-naphthylamine-6-sulphonic acid,2-naphthylamine-4:8-disulphonic acid, l-amino-8-naphthol-3:6-disulphonicacid, 2- amino-S-naphthol-7-sulphonic acid, Z-amino-S-naphthol-6-sulphonic acid, p-toluidine, m-anisidine, 2:4-dichloroaniline and alsodiamines such as ethylene diamine, p-phenylene diamine,4:4'-diaminostilbene-2:2'-disulphonic acid and 2:4- and2:5-diaminobenzene sulphonic acid, in addition to the above-noted azo oranthraquinone chromophoric group-containing amines.

In each instance, however, it will be remembered that there is at leastone halogen, preferably chlorine or bromine, atom on the ring (i.e. the6-position on the triazine ring always carries a halogen atom).

DESCRIPTION OF THE STABILIZING COMPONENT In the novel stabilizedcomposition provided by this invention, in addition .to at least one ofthe dyestuffs above-described being present as the principal coloringmatter, there is also present a stabilizer consisting essentially of amixture of phosphate salts. This mixture is advantageously composed onthe one hand of monosodium or mono-potassium phosphate salts and, on theother hand of dipotassium or disodium phosphate salt, but in generalthere may be used mixtures of monoand di-alkali metal salts ofphosphoric acid where the alkali metal is of Group IA of the periodicchart of the elements. As is well known, these salts may be mixed inproportions such that an aqueous solution thereof will have a bufferedpH lying between 6 and 8. It is these phosphate salt mixtures which areemployed in the composition of this invention (but not the mode ofpreparation of the phosphate salt mixture having the desired pH rangewhich is within the ability of those skilled in the art).

DESCRIPTION OF THE STABILIZED DYESTUFF COMPOSITIONS It has now beenfound that, when the subject class of dyestuffs are present in acomposition stabilized by the above-described phosphate salt mixture,that the storage characteristics of such dyestuffs are vastly improved,and can, in fact, be kept for extended periods of time under normaltemperature conditions whereas absent the phosphate stabilizing thedyestuffs would at least partially decompose, as already mentioned.Although the addition of even a trace of the phosphate salt mixturegives some improvement in storage stability of the dyestuffs, it ispreferred to add between 1% and 25% of the phosphate'salt mixture basedon the weight of the dyestulf, although the preferred mixture for eachparticular dyestutf will vary according to the particular groupingsattached to the'carbon atoms of the triazine nucleus present in thedyestuffs. For instance, where a 4:6-dihalogenotriazinyl dyestuff isused, it is preferred to use a mixture of the' phosphate salts which inaqueous solution will have a buffered pH lying between 6 and 7. Forexample, such a mixture would be one containing 7 parts of anhydrousdisodium hydrogen phosphate and 12.5 parts of anhydrous potassiumdi-hydrogen phosphate.

In practice thereof, it has been found that the addition of 10% byweight of the phosphate salt mixture relative to the weight of thedyestuff present in the composition usually'sufiices to give adequatestorage stability. The invention is, however, not to be understood asrestricted to compositions containing at least this amount.

The phosphate salt mixture may be added to the reaction mixture in whichthe dyestuff is formed either before or'during the reaction period, orit may be added after the reaction is completed but before the productis isolated. Where the reaction to prepare the dyestuff has been carriedout in aqueous suspension or solution, the phosphate salt mixture may beadded either in the solid state or in the form of an aqueous solution.When, during the isolation of the dyestuff, a filtration step isincluded and the separated solid is then washed on the filter with wateror an aqueous solution to remove impurities, the phosphate mixture mayconveniently be added to or dissolved in the water or aqueous solutionused to wash the separated solid. Advantageously, when the phosphatemixture is added to an aqueous solution or suspension, such suspensionor solution is made substantially neutral before addition of thephosphate mixture. Alternatively or additionally, the phosphate mixturemay be added to the dyestuff after isolation. This is especially usefulwhere the manufacture and isolation have been carried out undernon-aqueous conditions. The phosphate mixture may be added to thedyestuffs after isolation thereof by mixing or milling together thedyestuff and the phosphate mixture, and if desired, there may be addedother diluents which give neutral solution in water, for example ureaand sodium sulphate, as may be used for example in the manufacture ofdyestuif compositions of different tinctorial strengths.

In this latter connection, it will be understood that the preparatoryprocess of the invention, as described hereinafter and in theabove-mentioned copending applications, will frequently involve theisolation of the dyestuif proper in admixture with various inertdiluents, and it is frequently preferred to add inert diluents such ascommon salt, Glaubers salt, or urea, to give a dyestuff powdercontaining a standard proportion of dyestuff. With the subject class ofdyestuffs, it is convenient to limit them in compositions containing aslittle as perhaps 20% by weight of the dyestutf as such. The remainderof the composition may, if desired, consist entirely of the stabilizingphosphate salt mixture, or, more economically in many instances becomposed of inert Water-soluble solid diluents such as those mentionedabove together with the desired quantity of buffer. Accordingly, thisinvention contemplates and embraces compositions containing as little as20% by Weight of the subject class of dyestuffs and as much as 80% ofthe stabilizing phosphate salt mixture, and there being present at least1% based on the weight of the dyestufr', of the stabilizing phosphatesalt mixture.

Such compositions containing any of the mono-(C- halogeno) 1:3 :5triazin 2 ylamino-azo chromophoric group-containing dyestulf ormono-(C-halogeno)-1:3:5- triazin 2 ylamino anthraquinone chromophoricgroupcontaining dyestulf or di(C-halogeno)-1:325-triazin-2- ylamino-azochromophoric group-containing dyestulf or Idi-(C-halogeno)-1:3:5-triazin-2-ylamino anthraquinone chromophoricgroup-containing dyestuff, and the abovedescribed stabilizing phosphatesalt mixture, exhibit the improved storage characteristic advantagesprovided by this invention. These advantages are particularly wellexhibited with the compositions containing the di-(C-halogeno)-1:3:S-triazin-Z-ylamino-azo and anthraquinone chromophoricgroup-containing dyestuffs where the storage problem is somewhat moresevere than with the mono-halogens dyestuffs.

It is of interest that the action of the stabilizing phosphate saltmixture, which is a composition having a buffering characteristicappears to involve something more than mere buffering activity in thatother known buffers, which are effective buffers within the pH range ofsay from 6 to 8, fall to stabilize the subject class of dyestuffs whenincorporated in a composition in the same manner as that employed inthis invention. In fact, some of these other buffers actually seem tocatalyze the decomposition of the dyestuffs.

EXAMPLES OF THE INVENTION To further describe and explain thisinvention, the examples following hereinafter will illustrate typicalpreparations for the dyestuffs and the dyestuif compositions containingthe stabilizing phosphate salt mixture.

Example 1 A mixture of 31.9 parts of 1-amino-8-naphthol-3:6-disulphonicacid and 160 parts of water is stirred and sodium carbonate is addeduntil a clear solution which reacts alkaline to Brilliant Yellow paperis formed. This solution is added in 30 minutes at a temperature betweenC. and C. to a stirred suspension of cyanuric chloride formed by pouringa solution of 18.6 parts of cyanuric chloride in 100 parts of acetoneinto a mixture of 200 parts of water, and 300 parts of crushed ice and0.5 part of aqueous hydrochloric acid of specific gravity 1.18. Themixture is stirred for 30 minutes and there is then added a solution ofbenzene diazoniurn chloride obtained by dissolving 8.8 parts of anilinein 160 parts of water and 26.8 parts of aqueous hydrochloric acid ofspecific gravity 1.18, cooling the resultant solution to 0 C. and adding6.56 parts of sodium nitrite. Sodium carbonate is then added carefullyuntil the aqueous medium no longer reacts acid to Congo red paper andthen 100 parts of sodium chloride are added. In order to complete thecoupling more soda 18 ash is added gradually to raise the pH of theaqueous medium finally to about 7.7.

When no diazobenzene can be detected in the mixture, there is added toit a solution containing 7 parts of an hydrous disodium hydrogenphosphate and 12.5 parts of anhydrous potassium dihydrogen phosphate inparts of water and after stirring for another 15 minutes, the mixture isfiltered off. The residue is drained, mixed intimately with 4 parts ofanhydrous disodium hydrogen phosphate and 7.2 parts of anhydrouspotassium dihydrogen phosphate and dried at 40-45 C. A portion of thedyestuff so obtained is analyzed immediately after isolation. Theremainder is kept in a glass-stoppered bottle for 12 months and then asecond portion is analyzed. Less than 1% of the reactive chlorineattached to the triazine nucleus has been hydrolyzed.

Example 2 57.1 parts of the trisodium salt of the aminoazo compoundobtained by coupling d iazotized metanilic acid with1-acetylarnino-8-naphthol-3 :6-disulphonic acid in aqueous acid in thepresence of sodium carbonate and hydrolyzing the product so formed byheating with dilute caustic soda solution are dissolved in 800 parts ofwater at 20 C. The solution is added during 50 minutes to a stirredsuspension formed by pouring a solution of 18.6 parts of cyanuricchloride in 100 parts of acetone into 400 parts of Water and 60 0 partsof crushed ice. The mixture is stirred at a temperature below 4 C. After1 hour, sodium carbonate is gradually added to make the medium neutralto litmus. After another 30 minutes, sodium chloride is added at therate of 15 lbs. for every 10 gallons of mixture and the productprecipitated is filtered off, Washed with 15% brine solution and driedat 30 C. 3 parts of the dyestuff so obtained are thoroughly mixed with0.7 part of anhydrous disodium hydrogen phosphate and 1.25 parts ofanhydrous potassium dihydrogen phosphate and this mixture and theremainder of the dyestuif are stored for 28 months and portions of eachare analyzed.

It is found that only 3% of the reactive chlorine originally attached tothe triazine nucleus has been removed in the buffered sample but that66% of the chlorine originally attached to the triazi-ne nucleus hasbeen removed in the unbufiered sample.

Example 3 A solution containing the primary condensation prod not ofcyanuric chloride and the disodium salt of l-amino-8-hydroxy-napht-halene 3:6-disulphonic acid is obtained as described inExample 1. The solution is stirred for 30 minutes and there is thenadded a solution of the diazo compound from 14.25 parts ofp-aminoacet-anilide. Sodium carbonate is gradually added to the mixturein sufiicient amount to make the medium slightly alkaline to litmus andto keep it so during the next 6 hours. Salt is then added at the rate of12 lbs. for each 10 gallons of mixture and the product precipitated isthen filtered ofl, slurried with 400 parts of acetone, refiltered, andthen dried at 30 C. A mixture :of 3 par-ts of the dried dyestufi, 0.7part of anhydrous disodium hydrogen phosphate and 1.25 parts ofanhydrous potassium dihydrogen phosphate is made and this mixture andthe remainder of the dyestulf are stored for 28 months.

It is found that only 6% of the reactive chlorine originally attached tothe triazine nucleus in the buffered sample has been removed, but that98% of the chlorine originally attached to the triazine nucleus in theunbulfered sample has been removed.

Example 4 39.2 parts of2-chloro4-anilino-6(3'-amino-4-sulphoanilino)-s-triazine are stirredwith 600 parts of Water and sufiicient sodium carbonate is added to themixture to make it neutral to litmus. 30 parts of lON hydrochloric 1'3acid are then added and the temperature is adjusted between 15 C. and 20C. An aqueous solution of sodium nitrate is gradually added until aslight excess 1s present 5 minutes after the last addition. A solutioncontaining 30 parts of sodium acetate crystals in 160 parts of water isthen added. The mixture is then added over a period of 30 minutes to asolution containing 21.5 parts of1-(2"-chlorophenyl)-3-methyl-5-pyrazolone in 200 parts of water madejust alkaline to Clayton Yellow paper by addition of caustic soda. Themixture is stirred for 18 hours at a temperature between C. and C. andthen the precipitated product is filtered olf, mixed thoroughly with 4parts of anhydrous disodium hydrogen phosphate and 7.5 parts ofanhydrous potassium dihydrogen phosphate and then dried at 30 C. to givea yellow powder. The product is stored for 7 months at atmospherictemperature. Less than 1% of the chlorine originally attached to thetriazine nucleus is removed.

Example 5 A solution of 5.0 parts of cyanuric chloride in 24 parts ofacetone is poured gradually into a stirred mixture of 100 parts of waterand 100 parts of crushed ice. To the suspension of cyanuric chloride soobtained, a solution of 14.8 parts of the disodium salt ofl-fi-sulphatoisopropylamino-4-(4' aminoanilino) anthraquinone 3'-sulphonic acid is 300 parts of water is added during 1 hour, thetemperature of the reaction mixture being maintained between 0 C. and 2C. during the addition. The mixture is then stirred at this temperaturefor 1 hour during which time sufiicient 10% aqueous sodium carbonatesolution is added to maintain the reaction mixture neutral to litmus. Asolution of 6 parts of anhydrous disodium hydrogen phosphate and 12parts anhydrous potassium dihydrogen phosphate in 100 parts of water isadded to the mixture and then sufiicient sodium chloride is added at therate of 18 lbs. for each 10 gallons of solution. The mixture is warmedto 15 C. and stirred until precipitation of the dyestufi is complete andis then filtered. The dyestuif is washed on the filter with a solutionof 20 parts of sodium chloride, 1.5 parts of anhydrous disodium hydrogenphosphate and 3 parts of anhydrous potassium dihydrogen phosphate in 100parts of water, drained well, mixed thoroughly with 1 part of anhydrousdisodium hydrogen phosphate and 2 parts of anhydrous potassiumdihydrogen phosphate and dried at atmospheric temperature.

Example 6 32 parts of cyanuric bromide are dissolved in 280 parts ofdioxan at 65 C. The solution is poured into a stirred mixture of 200parts of water and 320 parts of crushed ice and to the suspension ofcyanuric bromide so formed there is added during 40 minutes a solutioncontaining 60.3 parts of the trisodium salt of l-amino- 2:3'z5 trisulpho4-(4'-aminoanilino)-anthraquinone in 1200 parts of water. The mixture isstirred at a temperature below 5 C. for 5 hours. During this period,sodium carbonate solution is added to the reaction mixture from time totime to keep it neutral to litmus. A solution containing 4.3 parts ofanhydrous disodium hydrogen phosphate and 7.7 parts anhydrous potassiumdihydrogen phosphate in 60 parts of water is added. 40 parts of sodiumchloride are then added and the mixture is stirred for minutes. Theprecipitated blue dyestuff is filtered off, washed on the filter with20% brine solution and drained well. The paste is mixed thoroughly with4.3 parts of anhydrous disodium hydrogen phosphate and 7.7 parts ofanhydrous potassium dihydrogen phosphate and dried at 30 C.

Example 7 A solution of 8.35 parts of cyanuric chloride in 40 parts ofacetone is added gradually to a stirred mixture of 170 parts of waterand 170 parts of crushed ice. The suspension of cyanuric chloride soobtained is stirred at a temperature between 0 C. and 4 C. and asolution of 22.2 parts of the disodium salt of1-amino-4-(4-aminoanilino)-anthra-quinone-2:3-disulphonic acid in 500parts of water is added during 1% hours. The mixture is stirred for afurther 45 minutes and then sufficient 10% sodium carbonate solution isadded gradually to render the reaction mixture neutral to litmus.Sufficient sodium chloride is then added to give a concentration ofgrams per liter of solution, and the mixture is stirred until separationof the dyestufi is complete and it is then filtered. The solid residueis washed with a 10% solution of sodium chloride in water, dried atatmospheric temperature and finally mixed intimately with a powderedmixture of 11.4 parts of anhydrous disodium hydrogen phosphate and 7.2parts of anhydrous potassium dihydrogen phosphate.

This dyestuif composition on storage for approximately 12 months in astoppered bottle at ordinary temperature was found to have lost only3.7% of its hydrolyzable chlorine content; a similar preparationcontaining no butter lost approximately 50% of its hydrolyzable chlorinecontent.

Example 8 A solution of 5 parts of cyanuric chloride in 24 parts ofacetone is added gradually to a stirred mixture of 100 parts of waterand 100 parts of crushed ice. The suspension of cyanuric chloride soobtained is stirred at a temperature between 0 C. and 4 C. and asolution of 13.33 parts of the disodium salt of1-amino-4-(3-aminoanilino)-anthraquinone-2:4'-disulphonic acid in 300parts of water is added over 1 hour. The mixture is stirred for afurther 1 hour and then sufiicient 10% sodium carbonate solution isadded gradaully to render the reaction mixture neutral to litmus. Asolution of 6 parts of anhydrous disodium hydrogen phosphate and 12parts of anhydrous potassium dihydrogen phosphate in 100 parts of Wateris added to the mixture, and after stirring for 10 minutes suificientsodium chloride is added to give a concentration of 200 grams per literof solution. The mixture is stirred for 1 hour and is then filtered. Thesolid residue is washed with a solution of 80 parts of sodium chloride,6 parts of anhydrous disodium hydrogen phosphate and 12 parts ofanhydrous potassium dihydrogen phosphate in 400 parts of water and isdried at atmospheric temperature. The dyestuff so obtained is mixedintimately with a mixture of 1 part of anhydrous disodium ydrogenphosphate and 2 parts of anhydrous potassium dihydrogen phosphate.

Example 9 A solution of 3.88 parts of cyanuric chloride in 20 parts ofacetone is added gradually to a stirred mixture of 60 parts of water and60 parts of crushed ice. To the suspension of cyanuric chloride soobtained there is added during 1 hour, a solution of 11.26 parts of thedisodium salt of1-amino-4-(3'-amin0-6'-methyl)-anilinoanthraquinone-2:4-disulphonic acidin 300 parts of water, the temperature of the reaction mixture beingmaintained between 0 C. and 3 C. during the addition. The mixture isthen stirred for 3 hours at 4 C. to 7 C. during which time it isinitially made neutral to litmus by the gradual addition of 10% sodiumcarbonate solution and subsequently maintained neutral by periodicaddition of 10% sodium bicarbonate solution. Sufficient sodium chlorideis then added to give a concentration of grams per liter and, afterstirring for about 30 minutes, a solution of 4 parts of anhydrousdisodium hydrogen phosphate and 8 parts of anhydrous potassiumdihydrogen phosphate in 50 parts of water is added. Sodium chlorideequivalent to a concentration of 40 grams per liter is added to assistaggregation and complete precipitation and, after stirring at 25 C. for30 minutes, the mixture is filtered; the product on the filter is Washedwith a solution of 40 parts of sodium chloride, 3 parts of anhydrousdisodium hydrogen phosphate and 6 parts of anhydrous potassiumdihydrogen phosphate in 200 parts of water and finally dried at roomtemperature.

Example 10 A solution of 4.84 parts of cyanuric chloride in 24 parts ofacetone is added gradually to a stirred mixture of 100 parts of crushedice. To the suspension of cyanuric chloride so obtained there is addedduring 45 minutes a solution of 13.68 parts of the disodium salt ofl-amino- 4-(3-amin0-2-methyl) anilinoanthraquinone-Z:5-disulphonic acidin 250 parts of water, the temperature of the reaction mixture beingmaintained between C. and 3 C. during the addition. The mixture is thenstirred for 2 hours at the same temperature during which time it is madeand maintained neutral to litmus by the gradual addition of 10% sodiumcarbonate solution. The temperature is raised to about 20 C., a solutionof 3 parts of anhydrous disodium hydrogen phosphate and 6 parts ofanhydrous potassium dihydrogen phosphate in 40 parts of water is addedand then sufficient sodium chloride is added to give a concentration of100 grams per liter. The mixture is stirred until separation of thedyestuif is complete and is then filtered. The dyestutf on the filter isWashed with a solution of 20 parts of sodium chloride, 3 parts ofanhydrous disodium hydrogen phosphate and 6 parts of anhydrous potassiumdihydrogen phosphate in 200 parts of water and finally dried at roomtemperature.

Example 11 32.0 parts of cyanuric bromide are dissolved in 280 parts ofdioxan at 65 C. and the solution so formed is added to a stirred mixtureof 200 parts of Water and 360 parts of crushed ice. There is then addedto the suspension so formed in 45 minutes a solution containing 50.6parts of the disodium salt of 1-amino-4-(3'-amino anilino)-anthraquinone2:4 disulphonic acid in 1000 parts of Water and the mixture is stirredat a temperature below 6 C. for 1 hours and then neutralized to litmusby careful addition of sodium carbonate solution. During the next 16hours, the temperature is still kept below 6 C. and further smallamounts of sodium carbonate solution are added as necessary to keep theaqueous reaction medium neutral to litmus. Salt is then added to give aconcentration of 250 grams per liter of volume and after a short timethe product precipitated thereby is filtered off, drained well, slurriedwith acetone, refiltered and washed on the filter with acetone. Thefilter cake so obtained is mixed with 12 parts of a mixture containinganhydrous potassium dihydrogen phosphate and anhydrous disodium hydrogenphosphate in the proportions of 125 to 70 and then dried at 30 C.Analysis shows that the isolated dyestuff contains 1.85 reactive bromineatoms in each molecule. When it is applied to cotton by the printing anddyeing processes described above, reddishblue shades having very goodfastness to wet treatments and to light are produced.

Example 12 A solution of the diazo compound from 27.3 parts of thesodium salt of 2-amino-4-sulphodiphenylether is added to a solutioncontaining the primary condensation product of cyanuric chloride and thedisodium salt of l-amino-S- hydroxynaphthalene-3:6-disulphanic acidprepared as described in Example 2 and the temperature of the mixture iskept below 5 C. Sodium carbonate is added gradually to raise the pH ofthe aqueous medium to 7 to 7.5 and keep it within this range untilcoupling is complete. This takes about 3 hours. Salt is then added tothe mixture at the rate of 5 lbs. for each 10 gallons of mixture andthen a solution of 4.2 parts of anhydrous disodium hydro"- gen phosphateand 7.5 parts of anhydrous potassium dihydrogen phosphate in 50 parts ofWater is added. After stirring the mixture for a short time, theprecipitated product is filtered off, mixed with 4.2 parts of anhydrousdisodium hydrogen phosphate and 7.5 parts of anhydrous potassiumdihydrogen phosphate and dried at 30 C. After 18 months storage atordinary temperature, the product so obtained has only lost 6% of thechlorine originally attached to the triazine nucleus.

If, in this example, the 27.3 parts of the sodium salt of2-amino-4-sulphodiphenyl ether are replaced by 28.6 parts of the sodiumsalt of 2-amino-3'-methyl-4-sulphodiphenyl ether then a similar dyestufiis obtained. After it has been stored at atmospheric temperature for 17months, only 6% of the chlorine originally attached to the triazinenucleus has been removed.

Additional teachings of suitable dyestuffs for use in the presentinvention, and further teachings of the methods of making the same maybe found in, for example, U.S. Patents No. 1,667,312, 1,704,637,1,779,398, 1,867,- 451, 2,270,478, and 2,399,066, and British Patent No.467,815.

As further examples of the compositions and advantages of thisinvention, Table 1, following, illustrates the typical superior storagecharacteristics achieved. In this table, the dyestuif obtained bycoupling diazotized 2- naphthylamine-4:8-disulphonic acid withm-toluidine and condensing with one molecular proportion of cyanuricchloride was stablized with various amounts of stabilizers whichconsisted essentially of mixtures of disodium hydrogen phosphate andpotassium dihydrogen phosphate at various pHs. The samples were storedat 60 C. in stoppered containers for 48 hours and then at C. for 24hours. The samples were analyzed and the following Table 1 summarizesthe results. In column I is given composition of stabilizer as ratio ofNa HPO to KH PO in column 11 is given initial pH of the mixture, incolumn III is given amount of stabilizer as a percentage of the totalcomposition, and in column IV is given loss in hydrolyzable chlorine asa percentage of the initial figure.

TABLE 1 1'. II III IV Percent Percent The extended storage life of thesubject dyestuffs as stabilized in compositions according to the presentinvention, Table 2 shows a comparison of two other dyestuffs which werestored for one year at 20 C. both as stabilized and as unstabilizedsamples. Dyestutf (1) is obtained by coupling diazotized5-amino-4-sulphoacetanilide with 1 (2'15' dichloro-4-sulphophenyl)-3-methyl-S-pyrazolone, hydrolyzing off the acetyl group and condensing theresultant aminoazo compound with one molecular proportion of cyanuricchloride. Dyestufi (2) is obtained by coupling diazotized aniline-2:5-disulphonic acid with l-(3-aminophenyl) 3-methyl-5- pyrazolone andcondensing the aminoazo compound obtained with one molecular proportionof cyanuric chloride. The second column gives the composition of thestabilizer expressed as a ratio of Na HPO to KH PO The third columngives the amount of stabilizer expressed as a percentage of the totalcomposition and the last column gives the amount of the reactivechlorine which has been lost expressed as a percentage of the initial,

o (2 TABLE 2 Dyestufi I II III Pcrcent (1) 1.1.77 10.0 (l) 0 l6 (2) 1-177 15 0 3.0 (2) 0 94 TABLE 3 In the first1-chloro-2-(dichlorotriazinylamino)-5-hydroxy-6-(Zgulphophenylazo)naphthalene-7-sulpnonic a i2-(dichlorotriazinylamino)-5-hydroxy-6-(4-methoxy-2-sulphoplienylazo)naphthalcne-7-sulphonic acid.

2-(dichloro-triazin-N-mcthylaniino)-5-hydroxy-6-(a-sulphophenylazo)naphtlialcne-B-sulphonic aei'2-(4'41ichlorotriazinylamino-T-acetyl-aminohcnylazo)naphthalene-:7-disulphonicacid.

4-( ichlorotriazinylamino-1 2 -azonaphthalenc 4:7:8-trisulphonic acid.

2-(4'-dichlorotriacinylamino-2-meth ylphenylazo) naphthalene-57-disulphonic acid.

1-(4'-sulphephenyl)-3-earboxy-4-(4-diehl0rotrliazinylamino-Z"-sulphophcnylazo)-5-pyraz-0 one.

1-(2 5-dichloro-4-sulphophenyl)-3-carboxy-4-(5"-dichlorotriazinylarnino-2-sulphophenylazo)-5-pyrazolone.

1(2 5-dichloroi sulphophenyl) -3-carboxy-4-(3-dichlorotriazinylaminophenylazo)-5-pyrazolone.

l-(3-dichlorotriazinylaminophcnyl)-3-mcthyl-4- (15"-disulpho-2"-naphthylazo)-5-pyrazolone.

The dyestufi obtained by coupling diazotised 4- amino-4-(7-sulphonaphtha(1:2:415) triazolyl-2 stilbene-Z:2-disulphonic acid with 1- (3-'uninophcnyl)-3-mctl1yl5-pyrazolone and condensing the aminoazo compound soobtained with one molecular proportion of cyanuric chloride. X

2-(dichlorotriazin-N-methylamino)-8-11ydroxy-7- (2Esulphophenylazo)naphthalcnc-G-sulphonic The dyestuli obtained bycoupling diazotised dehydrothio-p-toluidinc sulphonic acid underalkaline conditions with Z-(dichlorotriazin-N-methylarnine)-8-hydroxy-naphthalene-6su1- phonic acid.

2-(diclilorotriazin-N-methylamino)8-hydroxy-7-(4"-rnethoxy-2"-sulphoplienylazo naphtl1alencfi-sulphonic acid.

2-(dichlorotriazinylamino)-3-hydroxy-7-(2-sulphophcnylazo)naplithalene-G-sulphonicacid. 2-(dichlorotriazinylamino)-8-hydroxy-7-(l 5-disulpho-Z"-naphthylazo)naphthalenc-fi-sulphonic acid.2-(dichlorotriazinylamino)-8-hydroxy-7-(3-rnethoxy-5-sulphophenylazo)naphthalene-6- sulphonic acid.2-(dichlorotriazinylamino)-8-hydroxy-3-carboxy- 7-(2-S&11p110p11(5nylaZ0)HflphthQIQHC-G-SlllphOl'l- 1c aci1-diel1lorotriazin-N-methylamino)-5-hydroxy-6- (2-sulphopheny1aZ0)naphtha1eI1c-7-sulphonic acid.1-(3-dichlorotriazinylaminobcnzoylamino)-S-hydroxy-T-(2-sulphophenylazo)naphthalene- 3 :G-disulphonic acid.l-(3-dichlorotriazinylaminobenzoylamino)-8-hydroxy-7-(2"-sulphophenylazo)naphthalene- G-sulphonic acid.l-dichlorotriazin-N-ethylamino)-8-hydroxy-7-(4-mcthoxy-2sulphopl1enylazo)naphthalene 3:6-disu1phonic acid.1-(dichlorotriazin-N-ethylamino)-8-hydroxy-7-(4-mcthexyphenylazo)naphthalcnc-3:6- disulphonic acid.

TABLE 3-C0ntin'.ied

1-(3-dichlorotriazin-N-cthylamino)-8-hydroxy-7-(5-sulphamyl-1-naphthylazo)naphthalenc- 316-disulphonic acid.1-(dichlorotriazin-N-butylamino)-8-hydroxy- 2:7-azonaphthalene-1:316-trisulphonic acid.4-chlorc-4-(4dichlorotriazinylaininoplicnylazo)stilbene-2:2-disulph0nicacid.4-chloro4-(2-mcthyl-4-dichlorotriazinylarniuophenylazo)stilbene-2:2-disulphonicacid.-chloro-M-(4-dichloretriazin-N-rnethylamincaminophenylazo)stilbcne-Z:2-disulplionicacid.4-nitro-4-(2"-methyl-5"-mcthoxy-4-dichlorctriazinylamiuophenylazo)stilbcnc-2:2-disulphonic acid.4-nitro-4-(4"-dichlorotriazinylamino-7-sulphol-napl1thylazo(stillJcne-2:2-disulphonicacid. 4nitro-4-(4"-dichlorotriazinylaminophcnylazo)stilbene-Z:2'-disulphonic acid.4-(4-mcthoxyphenylazo)4-dichlerotriazlnylaminestilbene-2:2-disulphonicacid. 4-accl.ylamino-4-(4-dichlorotriazinylaminophenylazo)stilbene2z2-disulphonic acid.4-dimcthylamino,4-(2-mcthyl-4-dichlor0triazinylaminophcnylazo)sti1bene-2:2-disulphonicacid. 4-(7-sulplio-2"-naphtha(l:2:4:5)triazolyl)-4(4-diehlorotriazinylaminophenylazo)stilbene-2:2-disulphonic acid.

The dyestuff obtained by coupling diazotiscd iamino-1,(7-snlphonaphtha(1:2:4:5)triazolyl)- stilbcnc-2:2-disu]phonic acidwith 4-(3- methyl-l-pyrazol(5-)onyl-4-dichlorotriazinylaminostilbene-Z:2-disulphonic acid.

2-dibr0motriazinylamino-5-hydroxy-6-(2-sulphophcnylazo)naphthalenc-7-sulplionicacid.

2-dibroinotriazin-N-inethylan1ino-8-hydroxy-7- (2-5ulphophcnylazo)naphthalene-fi-sulpllonic 1 l-dibromotriazinylamino-B-hydroxy-7-(2-sulph phenylazomaphthalcne-BzG-disulphonic aci 1:8-dihydroxy2-(4-dichlorotriazinyla1nin0-2-sulphopllenylazomaphtlialc11c-316-disulp110nic ac2-hydroxy-l-(4-(lichlorotriazinylamino-2-sulphgphenylazo)naphthalene-6:8-disulphonieacil-phenylamino-8-hydroxy-7-(4-dichlorotriazinylamin0-2-sulphoplicnylazo)naphthalene-316-disulphonic acid. 1-bcnzoylamino-8-hydroxy-7-(4-triazinylamino-2-sulphopl1enylazo)naphthalcne-SzG-disulphonic acid.2-acctylamino-5-hydroxy-6-(4-dichlorotriazinylamino-2-sulpliophcnylazo)naphthulcne-7-sulphonicacid.l-benzoylamino-8-hydroxy-7-(5-dichlorotriazinylamino-2-sulphophcnylazo)naphthalene-3:6-diSulphonic acid.l-acetyliunino-8-hydroxy-7-(5-dicl1lorotriazinylamino-2-sulphophenylazo)naphthalene-3:G-disulphonic acid.

S-dichlorotriazinylamino-1-hydroxy-2:2-azonaphthalene-1:3zG-trisulphonic acid.

The copper complex of 2-diehloz'otriazinylaniin oa-hydroxy-fi(2-hydroxy-5-sulpllophcnylazo) naphtl1alenc-7-snlphonic acid.

The copper complex of l-dichlerotriuzinylamino-5hydroxy-G-(2-hydroxy-5-sulphophcnylazo) naphthalene-7-sulphonic acid.

The co per complex of l-dichlorotriazinylamino 8-hyroxy-7-(2-hydroxy-5-ethancsulpl1onylhonylazo)naphthalcnc-3:G-disulphonicacid.

The copper complex of 2-dichlorotriazinylamino-8-l1ydroxy-7-(2-hydroxy-5-sulphamylphcnyl azo)nap]lthalenc-fi-sulphonicacid.

The copper complex of 2-dichlorotriazinylainino-5-1lydroxy-fi-(2-hydroxy-5-sulphopncnylzao) naphthalene-l:7-disulphonicacid.

The copper complex of l-dichlorotriaziuylaniiuo-8-hydroxy-7-(2-hydrcxy-5-sulphophcnylazo) naphthalene-3 :G-disulphonicacid.

The copper complex of 1dichlorotriazinyl-ani111o-8-hydroxy-7-(2-hydroxy-4-(2"-sulphophenylao)phenylazo)napthalcne-3G-disulphonic aei 1-dicl1lor0triazinylamino-S-hydroxy-T-(2-incLhoxy-5-niethyl-4-(2-sulphophcnylazo)phenylazo)naphthalene-3:G-disulphonic acid.

l-dichlorotriaZinyIamino-Shydroxy-7-(2- rncthoxy-5-n1ethyl-4-(4 :8-disulpho-2 naphthylazo)pl1enylaz0)naphthalene-3 :G- disulphonic acid.2-(2-acctyla1nino-4-dichlorotriazinylaminophenylazo)naphthalene-4:S-disulphonicacid. fi-dichloro-triaziu-N-mcthylainino-l-hydroxy- 2 2-azenaphthalcnel:3 :5 -trisulpl1onie acid. 6-dichlorotriazinylainino-l-hydroxy-2:2-azonaphthalene-1 :3 5 :5-tetrasnlphonic acid.

TABLE 3-Continued I II III The 1:2 chrornium complex ofZ-diehlorotriazinylam1no-5-hydroXy-6-(2-carboxyphenylazo)naphthalene-7-sulphonic acid.

1:2 cobalt complex of 2-dichlorotriazinylamino-5-hydroxy-6-(2-hydroxy-3-nitro-5-sulpl1ophenylazo)naphthalene-7-sulphonicacid.

1 :2 chromium complex ofl-dichlorotriazinylamino-Z-hydrotry-7-(2-hydroxy-5-nitrophenylazo)naphthalene-3 G-disnlphonie acid.

1-amino2-sulpho4-dichlorotriazinylamino- 1 :2

anthraquinone.

1-(4-dichlorotriazinylamino) phenylamino- 1 :2

anthraquinone-2 :3-disulphonic acid.

1-an1i11o-2-sulphatoethoXy-4- (3-dieh1orotriazi- 1 :2

nylarnino-i-su1phophenylamino)anthraquinone.

l-cyclohexylarnino-et-(4-dichlorotriazinylamino- 1:2

phcnylamino)anthraquinone-3 :G-disulphonic aci 1 :4-bis(3-dichlorotriazinylamino-4-sulpho- 1 :2

phenylarnino)anthraquinone.

9. (4-dich1orotriazinylamino-2 -su lphophenyl) 1 :2

3 :4-phthaloylacridone-lO-sulphonie acid.

2-(2-hydroxy-5-sulphophenyl)-6-(4 -dichloro- 1 :2

triazinylamino-3-sulphophenylamino) -1 :9- anthrapyrirnidine.

It will be apparent that within the principles disclosed above thisinvention may be practiced according to various specific dyestufis andcompositions, including those specifically shown as well as others whichwill be obvious to one skilled in the art reading this disclosure.Accordingly, our invention is limited only by the spirit and scope ofthe following claims.

We claim:

1. Solid dyestufl compositions containing as the principal coloringmatter the substantially neutral alkali metal salt of a dyestufi'selected from the class consisting of azo and anthraquinone dyestuffscontaining at least one ionogenic solubilizing group and an amino groupselected from the class consisting of primary and secondary amino groupscarrying as N-substituents a 1:3:5-triazine radical containing twohalogens, selected from the group consisting of chlorine and bromineatoms attached to the carbon atoms of said triazine ring, and astabilizer for said dyestuff consisting essentially of a mixture ofwatersoluble alkali metal salts of phosphoric acid, which mixture has anaqueous solution a pH of from 6 to 8, wherein said alkali metal isselected from the group consisting of sodium and potassium.

2. The composition of claim 1, wherein said composition also contains aninert diluent in addition to said dyestufi and said mixture ofwater-soluble phosphate salts.

3. The composition of claim 1, wherein said dyestuff is an azo dyestuifand said 1:3:5-triazine radical carries two halogen atoms attached tothe carbon atoms of the triazine ring.

4. The composition of claim 1, wherein said dyestufi is an anthraquinonedyestufi and said 1:3:Shtriazine radical carries two halogen atomsattached to the carbon atoms of the triazine ring.

References Cited in the file of this patent UNITED STATES PATENTS Gubleret al. Aug. 1, 1939 Libby et al Oct. 24, 1 944 OTHER REFERENCES

1. SOLID DYESTUFF COMPOSITONS CONTAINING AS THE PRINCIPAL COLORINGMATTER THE SUBSTANTIALY NEUTRAL ALKALI METAL SALT OF A DYESTUFF SELECTEDFROM THE CLASS CONSISTING OF AZO AND ANTHRAQUINONE DYESTUFFS CONTAININGAT LEAST ON EIONOGENIC SOLUBILIZING GROUP AND AN AMINO GROUP SELECTEDFROM THE CLASS CONSISTING O FPRIMARY AND SECONDARY AMINO GROUPS CARRYINGAS N-SUBSTITUENTS A 1:3:5-TRIAZINE RADICAL CONTAINING TWO HALOGENS,SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE ATOMSATTACHED TO THE CARBON ATOMS OF SAID TRIAZINE RING, AND A STABILIZER FORSAID DYESTUFF CONSISTING ESSENTIALLY OF A MIXTUR OF WATERSOLUBLE ALKALIMETAL SALTS OF PHOSPHORIC ACID, WHICH MIXTURE HAS AN AQUEOUS SOLUTON APH OF FROM 6 TO 8, WHEREIN SAID ALKALI METAL IS SELECTED FROMTHE GROUPCONSISTING OF SODIUM AND POTASSIUM.